464687 Α7 Β7 經濟部中央標準局員工消費合作社印製 五、發明説明 本發明係關於一種催化劑組合物及關於在加氫轉化方法 中其之用途’於方法中包含芳族化合物之一種烴油係於此 種催化劑組合物之存在下與氫接觸。用於製備催化劑組合 物之一種方法亦形成未發明之一部分。 加氫處理催化劑於此技藝中係熟知的。習用之加氫處理 催化劑包含承載於—種耐火氧化物載體上之至少一種族 VIII金屬成分及/或至少—種族vIB金屬成分。該族VIII金屬 成分可係以一種非-賁金屬爲主，諸如鎳（Ni)及/或軲（co)， 或可係以一種貴金屬爲主，諸如鉑（pt)及/或鈀有用 之族VIB金屬成分包括以鉬（Mo)及鎢（W)爲主者。最通常應 用之耐火氧化物載體材料係無機氧化物諸如矽石、氧化鋁 及矽石-氧化鋁及鋁矽酸鹽類，諸如改質之沸石γ。習用之 加氫處理催化劑之特定實例係NiMo/氧化鋁、CoMo/氧化 鋁' NiW/矽石-氧化鋁、Pt/矽石-氧化鋁、PtPd/矽石一氧 化鋁、P t/改質之沸石γ及PtPd/改質之沸石γ。 加氫處理催化劑通常係使用於其中以氫接觸一種烴油進 料以降底其之芳族化合物、硫化合物及/或氮化合物之含量 之方法中。通常，其中芳族烴含量之降低係主要目的之加 氫處理方法係稱爲氫化方法，而主要集中於降低硫及/或氮 含量之方法係分別地稱爲加氫脱疏及加氫脱氮方法。現行 之環境標準要求石油產品之芳族烴含量及硫與氮含量皆很 低及通常預期在未來芳族烴、硫及氮之規格將變成愈來愈 嚴格。於是，於烴油餾分之精煉中，強烈地氫化、強烈地 加氫脱硫及強烈地加氫脱氣之能力將變成逐漸地重要的。 本紙張尺度適用中國國家標隼（CNS ) A4規格（2l〇X297公釐） ----------f------"------線 (請先閲讀背面之注意事項r4寫本頁) , 」 經濟部中央橾率局員工消費合作. 社印製 464687 A7 _______ B7 五、發明説明# ) 單核芳族（monoaromatic)化合物之有效氫化通常係難以用 習用之加氫處理催化劑達成。在另一方面，習用、專用之 芳族烴氫化作用催化劑通常具有相對地低之硫及/或氮允許 量’以使彼等於實質數量之含硫及/或含氮之化合物之存在 下顯示不良之氫化作用活性。爲了此種原因，用於降低芳 族烴及含硫與含氮之化合物之數量之習用方法係一種兩階 段方法，具有第一加氫脱硫及/或加氫脱氮階段及，通常於 移除生成之硫化氫及氨之後，用於氫化仍然留下之芳族烴 之第二階段。 本發明針對提供一種加氫處理催化劑，其顯示優良之芳 族烴氫化作用活性，而同時具有優良之加氫脱硫作用及/或 加氫脱氮作用活性。於是，此意指催化劑组合物於實質數 量之含硫及含氮之化合物之存在下應能有效地促進芳族烴 之氫化作用。本發明另外針對提供對於單核芳族烴顯示優 良之氫化作用活性之一種加氫處理催化劑。將須瞭解，於 加氫處理方法中此種催化劑之使用提供滿足用於（單核）芳 族烴、硫及氮之未來之低含量規格之一種更多之潛能。 於是’於第一種態樣中本發明係關於包含承載於一種酸 性載體上之以重量計0.1至1 5%之選自鉑 '鈀及銥之—種或 一種以上之一種貴金屬、及以重量計2至40%之錳及/或錁 之一種催化劑组合物，該重量百分比表示以載體之總重量 爲基準之金屬之數量。 錳及鍊皆屬於元素週期表之族ViIB。第三種族VnB金 屬’饍’由於其之不要定性’如熟諳此技藝者將注意到， -5- 本紙張尺度適用中國國家標準（CNS )八4说格（2S0X297公疫) ~ ---------------1Τ------線 (請先閱讀背面.之注意事項r〜寫本頁) - 464687 經濟部中央標隼局負工消費合作社印製 A7 ___B7__五、發明説明（3 ) 因此係無用的°催化活性之金屬，即一方面鉑及/或把及/ 或敏、及另一方面叙及/或銖，可係以元素形式、如一種氧 化物、如一種疏化物或如兩種或兩種以上之此等形式之混 合物存在。如於後文中將詳細地討論，使用以製備本催化 劑之一種適合之製備方法包括於空氣中烺燒之最後階段， 其將致使催化活性之金屬係至少部分地轉化成爲彼等之氧 化物》通常此種最後烺燒階段將致使實質上所有之催化活 性之金屬轉化成爲彼等之氧化物。倘若其後用一種含硫之 進料接觸催化劑’則至少部分之此等氧化物將係硫化及因 此轉化成爲對應之硫化物（"當場"硫化作用）。於此化種情 況中’已觀察到很良好之催化劑性能及因此認爲使催化活 性之金屬至少部分地如硫化物存在於催化劑中係本發明之 一種較佳具體實施例。於是，催化劑於與進料接觸之前亦 可將其經歷一種分別之預硫化處理。金屬氧化物之硫化作 用之程度可係由相關之參數控制，諸如溫度及氫、硫化 氫 '水及/或氧之分壓。金屬氧化物可係完全地轉化成爲對 應之硫化物’但適合地於催化活性之金屬之氧化物與疏化 物之間將形成一種平衡狀態，以使催化活性之金屬係如氧 化物及如硫化物兩者存在ίϊ 如於以下將較詳細地討論，根據本發明之催化劑可適合 地使用於各種之加氫轉化方法中。已發現，於製氣油^熱及/ 或催化裂解之蒸餾油（諸如輕循環油及裂解循環油）及兩種 或兩種以上之此等油之混合物;之加氫處理中，此種催化劑 係特別有用的。此等油通常包含相對地大之數量之芳族化 -6- 表紙張从適财關家辟(CNS ) A4jm ( 2ί〇Χ297/^¾ ) (請先閲讀背面之注意事項71¾本I) 裝- 訂 線· 經濟部中央標準局員工消費合作社印製 β 8 7 Α7 -- ----------------------Β7 五、發明説~~) ' "— 合物、含硫之化合物及含氮之化合物。由於環境之規格， 因此通常必須降低此等化合物之數量。對於達到某些技術 貝規格，諸如於α車製氣油之實例中之十六燒値 '於噴 射機燃油之案例中之煙點及於潤滑油餾份之案例中之顏色 及安定性，降低芳族化合物亦可係需要的。當於製氣油（熱 及/或催化裂解之备館油及兩種或兩種以上之此等油之混合 物）之加氫處理中使用根據本發明之催化劑時，對於例如符 合汽車製氣油規格之需要之降低可係於單—階段中擭得。 已發現，縱然於實質數量之含硫及含氮之化合物之存在 下，本發明之催化劑對於降低於最後產物中之單核芳族烴之 數量仍然係特別活性的。 根據本發明之催化劑包含以重量計〇丨至丨5 %之鉑及/或把 及/或銥及以重量計2至40%之錳及/或錁作催化活性之金 屬。倘若使用較低數量之催化活性金屬，則催化劑之活性 變成太低以致於係商業上不吸引人的。在另一方面，僻若 催化活性金屬之數量係比指示之上限較高，則於催化活性 中之進一步之增加不値得另外數量之金屬之成本。特定言 之，此應用於銘及紐。以包含以重量計3至之貴金属 (即始及/或鈀及/或銥）及以重量計2 (較佳地5 )至30%之錳 及/或銖之催化劑，可擭得良好之結果。 關於貴金屬成分’最好僅使用把，而關於叙及鍊，鍊係 較佳之金屬。於是，一種很較佳之催化劑係包含鈀及鍊作 爲催化活性金屬之一種催化劑。 使用以承載催化活性金屬之載體係一種酸性載體。酸性 本纸張尺度適用中國國家標準（CNS ) Α4规格（2丨0乂297公釐） K-1J .". ------ ---1--—! I (請先閲讀背面之注意.事項本頁)464687 Α7 Β7 Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs 5. Description of the invention The invention relates to a catalyst composition and its use in a hydroconversion process. 'A hydrocarbon oil containing aromatic compounds in the process is based on This catalyst composition is contacted with hydrogen in the presence. One method for preparing the catalyst composition also forms part of the uninvented. Hydrotreating catalysts are well known in the art. Conventional hydrotreating catalysts include at least one Group VIII metal component and / or at least an ethnic vIB metal component supported on a refractory oxide support. The Group VIII metal component may be based on a non-rhenium metal such as nickel (Ni) and / or europium (co), or may be based on a precious metal such as platinum (pt) and / or palladium. The VIB metal composition includes mainly molybdenum (Mo) and tungsten (W). The most commonly used refractory oxide support materials are inorganic oxides such as silica, alumina, and silica-alumina and aluminosilicates, such as modified zeolite gamma. Specific examples of conventional hydroprocessing catalysts are NiMo / alumina, CoMo / alumina 'NiW / silica-alumina, Pt / silica-alumina, PtPd / silica-alumina, P t / modified Zeolite γ and PtPd / modified zeolite γ. Hydrotreating catalysts are generally used in processes in which a hydrocarbon oil feed is contacted with hydrogen to reduce its aromatic, sulfur, and / or nitrogen content. In general, the hydroprocessing method in which the reduction of aromatic hydrocarbon content is the main purpose is called a hydrogenation method, and the method mainly focused on reducing the sulfur and / or nitrogen content is called hydrodesulfurization and hydrodenitrogenation, respectively method. Current environmental standards require very low aromatic hydrocarbon content and sulfur and nitrogen content of petroleum products and it is generally expected that the specifications of aromatic hydrocarbons, sulfur and nitrogen will become more stringent in the future. Thus, in the refining of hydrocarbon oil fractions, the ability to strongly hydrogenate, strongly hydrodesulfurize, and strongly hydrodegas will become increasingly important. This paper size is applicable to China National Standard (CNS) A4 (2l0 × 297mm) ---------- f ------ " ------ line (please read first Note on the back of r4 write this page), "" The Central Government Bureau of the Ministry of Economic Affairs, consumer cooperation. Printed by the agency 464687 A7 _______ B7 V. Description of the invention #) The effective hydrogenation of monoaromatic compounds is usually difficult to use. The hydrotreating catalyst was achieved. On the other hand, conventional, dedicated aromatic hydrocarbon hydrogenation catalysts often have relatively low allowable amounts of sulfur and / or nitrogen to make them appear poor in the presence of a substantial amount of sulfur and / or nitrogen-containing compounds. Its hydrogenation activity. For this reason, the conventional method for reducing the amount of aromatic hydrocarbons and sulfur- and nitrogen-containing compounds is a two-stage process, which has a first hydrodesulfurization and / or hydrodenitrogenation stage and is usually removed After the generated hydrogen sulfide and ammonia, it is used for the second stage of hydrogenation of the aromatic hydrocarbons that remain. The present invention is directed to provide a hydrotreating catalyst which exhibits excellent hydrogenation activity of aromatic hydrocarbons, and at the same time has excellent hydrodesulfurization and / or hydrodenitrogenation activity. Thus, this means that the catalyst composition should be able to effectively promote the hydrogenation of aromatic hydrocarbons in the presence of substantial amounts of sulfur- and nitrogen-containing compounds. The present invention is further directed to providing a hydrotreating catalyst which exhibits excellent hydrogenation activity against mononuclear aromatic hydrocarbons. It will be appreciated that the use of such catalysts in hydroprocessing methods provides one more potential to meet future low content specifications for (mononuclear) aromatic hydrocarbons, sulfur and nitrogen. Thus, in the first aspect, the present invention relates to a kind comprising one or more precious metals selected from platinum, palladium and iridium, and containing 0.1 to 15% by weight, supported on an acidic support, and the weight A catalyst composition of 2 to 40% of manganese and / or rhenium, the weight percentage indicates the amount of metal based on the total weight of the support. Manganese and chains belong to the family of the periodic table ViIB. The third race VnB metal 'diet' is not qualitative due to its lack of quality. 'As the person skilled in this art will notice, -5- this paper size is applicable to Chinese National Standard (CNS) 8-4 grid (2S0X297 public epidemic) ~ ---- ----------- 1T ------ line (please read the note on the back first ~ write this page)-464687 Printed by A7 ___B7_ V. Description of the invention (3) Therefore, it is a useless metal with catalytic activity, that is, platinum and / or succinate on the one hand and / or sensitization on the other, and / or baht, on the other hand, can be in the form of an element, such as an oxidation A substance, such as a phosgene, or a mixture of two or more of these forms, is present. As will be discussed in detail later, a suitable preparation method used to prepare the catalyst includes the final stage of calcination in air, which will cause catalytically active metal systems to at least partially convert into their oxides. This final calcination stage will result in the conversion of substantially all catalytically active metals to their oxides. If the catalyst is subsequently contacted with a sulfur-containing feed, at least part of these oxides will be sulfided and thus converted into corresponding sulfides (" on-site " sulfidation). In this case, very good catalyst performance has been observed and it is therefore considered that the presence of catalytically active metals in the catalyst at least partly as sulfides is a preferred embodiment of the present invention. Thus, the catalyst can also be subjected to a separate presulfidation treatment before it comes into contact with the feed. The degree of sulfidation of metal oxides can be controlled by related parameters, such as temperature and partial pressure of hydrogen, hydrogen sulfide 'water and / or oxygen. Metal oxides can be completely converted into the corresponding sulfides', but an equilibrium state will be formed between the oxides of the catalytically active metals and the sulfides, so that the catalytically active metals such as oxides and such as sulfides Both exist. As will be discussed in more detail below, the catalyst according to the present invention can be suitably used in various hydroconversion processes. It has been found that such catalysts are used in gasification oils and thermally and / or catalytically cracked distillation oils (such as light cycle oils and cracked cycle oils) and mixtures of two or more of these oils; Department is particularly useful. These oils usually contain a relatively large amount of aromatic-6-sheet paper from CNS A4jm (2ί〇Χ297 / ^ ¾) (please read the precautions on the back first 71¾ this I) Printed by the Consumers 'Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs β 8 7 Α7----------------------- B7 V. Inventions ~~)' "-Compounds, sulfur-containing compounds and nitrogen-containing compounds. Due to environmental specifications, it is often necessary to reduce the number of these compounds. For reaching certain technical specifications, such as the sixteen burns in the case of alpha car gas oil, the smoke point in the case of jet fuel and the color and stability in the case of lubricating oil fraction, reduce Aromatic compounds are also desirable. When the catalyst according to the invention is used in the hydrotreatment of gas-generating oils (thermal and / or catalytic cracking equipment oils and mixtures of two or more of these oils), for example, automotive gas-generating oils The reduction in specification requirements can be achieved in a single stage. It has been found that the catalysts of the present invention are particularly active in reducing the amount of mononuclear aromatic hydrocarbons in the final product, even in the presence of substantial amounts of sulfur- and nitrogen-containing compounds. The catalyst according to the invention comprises from 0 to 5% by weight of platinum and / or from and / or iridium and from 2 to 40% by weight of manganese and / or rhenium as catalytically active metals. If a lower amount of catalytically active metal is used, the activity of the catalyst becomes too low to be commercially attractive. On the other hand, if the amount of the catalytically active metal is higher than the indicated upper limit, a further increase in catalytic activity will not result in the cost of another amount of metal. In particular, this applies to Ming and New Zealand. Good results can be obtained with catalysts containing 3 to by weight of precious metals (ie, starting and / or palladium and / or iridium) and 2 (preferably 5) to 30% by weight of manganese and / or baht. . Regarding the precious metal component ', it is preferable to use only a handle, and as for the chain, the chain is preferably a metal. Therefore, a very preferable catalyst is a catalyst containing palladium and a chain as a catalytically active metal. The carrier used to carry the catalytically active metal is an acidic carrier. Acidity This paper is in accordance with Chinese National Standard (CNS) Α4 specification (2 丨 0 乂 297 mm) K-1J. &Quot;. ------ --- 1 --—! I (Please read the back first (Notes on this page)
*1T 經濟部中央標準局員工消費合作社印製 464687 A7 ________B7 五、發明説明（5 ) 載體於此技藝中係已知的。因此，對於本發明之目的，適 用之載體之實例包括包含一種鋁矽酸鹽或矽鋁嶙酸鹽滩 石、非晶形矽石-氧化鋁、氧化鋁、氟化之氧化鋁、頁矽酸 鹽或兩種或兩種以上之此等物質之—種混合物之酸性載 體。將須注意者，使用之酸性載體之類型主要地係視催化 劑之計畫用途而定。然而’對於大多數之用途，最好載體 包含一種沸石。適用之沸石之實例係矽鋁磷酸鹽，諸如 SAPO-l 1、SAP0-31、及SAP0-41及銘碎酸鹽滩石如鎂絵彿 石、ZSM-5、ZSM-23、SSZ-32、絲光沸石、貝他-涛石及八 面滞石類裂之海石諸如八面浠石及合成滞石γ。當於製造 潤滑基礎油、包括一種加氫轉化階段之一種方法中使用本 催化劑時，可考慮，例如，矽鋁磷酸鹽之使用。然而，就 大體而論，鋁矽酸鹽沸石之使用係較佳的。一種特別較佳 之鋁矽政鹽沸石係沸石Y，其通常係以一種改質（即脱銘） 之形式使用。特定言之當使用根據本發明之催化劑作爲降 低芳族烴及含硫及含氮之化合物之含量之一種加氫處理催 化劑時，使用包含一種改質之沸石Y之一種酸性載體係很 較佳的。一種特別有用之改質之沸石Y係具有低於24 6〇埃 (較佳地24·20至24.45埃及更佳地24·20至24.35埃）之單位晶 胞尺寸及於5或10至〗50(例如自5、10或15至或自5、 10、15或30至90)之範園内之Si02/Al203莫耳比者。此等 載體於此技藝中係已知的及實例係，例如，於歐洲專利_八- 0,247,678 ;歐洲專利-A-0,303,332 :及歐洲專利-A-0,512,652 中敘述。亦可適合地使用具有增加絵金屬（通常係鈉）含量 -8- 本紙張尺度適用中國國家標準（CNS ) A4说格（210X297公釐） ' '' f 裝 訂 線 {請先閱讀背面之注意·事項ri..w本頁) 經濟部中央標準局員工消費合作社印製 dG4687 A7 ----—____Β7 五、發明説明（e ) 之改質 <讳石γ ’諸如於歐洲專利_八_〇,519,573中敘述者。 ”除了任何之上述載體材料以外，載體亦可包含一種黏合 Μ材科。於催化劑載體中黏合劑之使用於此技藝中係熟知 f及’因此，適用之黏合劑包括無機氧化物，諸如矽石、 乳化銘、碎石、氧化鋁、氧化硼、氧化锆、及氧化鈦、及 黏土。於此等中，對於本發明之目的，矽石及/或氧化鋁之 ^用係較佳的。倘若存在，則以載體之總重量爲基準，載 體之黏合劑含量可於以重量計5至95%變動。於一種較佳具 體只施例中，载體包含以重量計1 0至60%之黏合劑。已發 現，以重量計10至40%之黏合劑含量係特別有利的。 根據本發明之催化劑可係使用於各種之加氫轉化方法 中其中包含芳族化合物之一種烴進料係於高溫度及壓力 氫之存在下與催化劑接觸，此等方法之特定實例係加氫 衣解、潤滑油製造（加氬裂解/加氫異構化）及加氫處理。 灰是，本發明亦係關於在一種方法中上述之催化劑之用 途，於方法中包含芳族化合物之一種烴進料係於高溫度及 壓力於氫之存在下與催化劑接觸。由於本催化'劑不僅於加 氫處理芳族化合物中、而且於移純及/或氮化合物中係有 政的’因此包含除了芳族化合物以外，含疏及/或含氮之化 合物之烴進料係特別適合的s 由於根據本發明之催化劑之優良之加氫處理性能，因此 根據本發明之催化劑作爲於一種兩階段加氫裂解方法中之 第階段催化劑係特別有用的。然後，第二階段催化劑係 一種專用之加氫裂解催化劑。 _____-9- 本紙張尺度適用中國國私標準（CNS ) A4規格（21〇 X297公楚;） ----------夢------1Γ------Φ (諳先閲讀背面.之注意事項rllsr本頁) 464687 A7 B7 經濟部中央標準局員工消资合作杜印製 五、發明説明（7 ) 於潤滑基礎油製造方法中’可包括至少一種加氫轉化階 段’以自進料移除含硫及/或氮之污染物、及/或氫化芳族 化合物、及/或加氫異構化直鏈及略微分枝之烴成爲進一步 分枝之烴、及/或加氫裂解蠟狀分子（通常係長鏈石壤分子 或包含此種類型之尾部之分子）成爲較小分子。對於在此等 潤滑基礎油製造方法中之用途，根據本發明之催化劑較佳 地將包含一種載體’其包含非晶形之矽石—氧化鋁、襄化之 氧化紹或具有《夕石及/或氧化銘作爲黏合劑之一種沸石。倘 若計畫主要發生加氫處理反應，則包含改質之沸石γ之載 體之使用係較佳的。倘若蠟狀分子之裂解及/或加氫異構化 作用係主要目的’則較佳之載體包含氟化之氧化鋁、非晶 形矽石-氧化鋁或滞石，諸如鎂鹼滞石、ZSM_5、2SM-23、 SSZ-32及SAPO-Π。於一種潤滑基礎油製造方法中之一種 加氫轉化階段通常包含於在200與450°C之間之溫度及至多 200巴之壓力下用一種適合之催化劑於氫之存在下接觸—種 潤滑油進料。其中可使用根據本發明之催化劑之潤滑基礎 油製造方法之實例係揭示於英國專利_Α_1ι546>5〇4及歐洲專 利-Α-0,178,710 中。 已發現，根據本發明之催化劑係特別適合於在—種加氫 處理方法中之使用。適合之加氫處理操作條件係於20〇至 450°C(較佳地210至350或400°C)之範圍内之溫度、及於10 至200巴（較佳地25至100巴）之範圍内之總壓力。適合之加 氩處理方法之實例係已於歐洲專利申請案公告第〇,553,92〇 號及0,611,816號中敘述。用於此種加氫處理方法之適合之 -10- ----------^------ΪΤ------^ (請先閲讀背面之注意事項寫本頁) - 本紙張尺度適用中國國家榡準（CNS > A4規格（210X297公釐） A7 B7 五 、發明説明（8 ) 經濟部中央橾準局員工消費合作社印製 進料係催化裂解之汽油、製氣油、輕製氣油、熱及/或催化 裂解之蒸餾油（諸如輕循環油及裂解循環油）及兩種或兩種 以上此等油之混合物。多種之此等進料通常包含以重量計 至少70%之於150與450°C之間沸騰之烴。當使用於此種加氫 處裡催化劑中時’最好載體以於以上表示之數量包含一種 黏合劑於加氫處理之案例中，於載體中之較佳酸性材料 係一種铭碎故鹽沸石’最佳係改質之沸石γ。已發現，縱 然於實質數量之含硫及含氮之化合物之存在下，本催化劑 仍然顯示優良之加氫處理活性及對於加氫處理單核芳族烴 係特別有效的。此外，本催化劑對於雙核芳族烴及較高級 芳族烴（二或二以上多核芳族烴）之氫化亦係很有效的。 本發明亦係關於製備上述之催化劑之一種方法，其方法 包含適合地經由浸潰或離子交換技術、接著乾燥及愤燒及 視需要預硫化而組合催化活性之金屬進入耐火氧化物載體 中。爲了獲得具有特別良好之催化活性之催化劑，本方法 可係經由下列階段而進行： (a) 用包含選自鉑 '鈀及銥之化合物之一種貴金 合物之 -種或-種以上溶液、及包含—㈣仏切化合物之一種 或-種以上溶液浸潰載體，視需要具有中間之乾燥及/或愤 燒；及 (b) 於在2观6贼之範圍内之溫度乾燥及娘燒如此經浸潰 之載體。 、 浸潰載體之-種較佳方法係所謂孔隙體積方法，其包括 用茱種體積之浸潰溶液處理一種載體，其中浸潰溶液之該 -11 本紙浪尺度適用中國國家標準（CNS ) A4規格（210X297公釐 (請先閲讀背面之注意事項-,.Ι,ΦΓ本頁j 袭 訂 ------線--- I --- 4 S 4 6 8 經濟部4-央標準局員工消费合作社印製 Α7 Β7 五、發明説明（9 ) 體積實質上係等於載體之孔隙體積。以此種方式，達成浸 漬溶液之完全使用。已發現，由於生成之催化劑顯示特別 良好之性能，因此此種浸潰方法係特別適合於本發明之目 的。浸潰階段（a)可係使用包含所有金屬成分之一種浸漬溶 液進行或可係以兩個分別之浸潰階段進行，用於以鉑及/或 鈀及/或級之浸潰之一階段及用於以錳及/或铼浸潰之一階 段，可能地具有一種中間乾燥及/或烺燒階段。 於用於製備根據本發明之催化劑之浸潰溶液中可使用之 金屬化合物，係於此技藝中已知的。典型之錳化合物係可 溶於水中之其鹽類，諸如硫酸錳、硝酸錳及醋酸錳。典型 之銖化合物係過錁酸、過鍊酸銨及過銖酸鉀。於浸潰溶液 中使用之典型之鈀化合物係四氣鈀酸（H2PdCl4)、硝酸鈀、 氣化鈀（II)及其之胺錯合物。H2PdCl4t使用係較佳的。於 一種浸潰溶液中使用之典型之鉑化合物係視需要於氫氣酸 之存在下之六鼠銘酸（H2PtCl6)、氫氧化翻胺及適合之銘胺 錯合物。 於催化劑製備中於最後階段中將催化劑於空氣中娘燒、 因而使金屬成爲彼等之氧化物之形式，係—般之常例。爲 了將金屬至少部分地轉化成爲彼等之硫化物，催化劑可係 於最後娘燒階段之後及於與進料接觸之前預硫化^適合之 預硫化方法於此技藝中係已知的，諸如例如自歐洲專利申 请案公告弟 0，181，254 號；〇,329,499 號；〇,448,435 號及 〇,564,317號及國際專利申請案公告世界智慧所有權组織專 利第93/02793號及世界智慧所有權组織專利第94/25157號。 -12- 本紙張尺度適用中國國家揉準（CNS ) A4規格（2丨Οχ297公着） ¾1T------.^ (請先閣讀背面之注意事項再本瓦) 經濟部中央標準局員工消費合作社印製 A7 B7 五、發明説明（ίο ) 於是’於本發明之另一種具體實施例中，製備催化劑之方 法包含下列之另外階段： (c)將經乾燥及經烺燒之催化劑經歷一種預硫化處理。 除了前述之預硫化方法以外，預硫化亦可係經由當場預 硫化作用而發生。此包括用一種含硫之烴進料於適合之條 件下接觸經娘燒之催化劑，適合之條件通常係比於擬想之 操作之期間施用之條件較不劇烈。 根據本發明之催化劑可係經由於此技藝中已知之方法而 再生。用於自廢催化劑回收催化活性之金屬之一種典型方 法包含自反應器移出去活化之催化劑、洗滌催化劑以移除 烴' 燒掉焦碳及其後回收貴金屬及錳及/或錁。 本發明係經由下列實例而舉例説明，但本發明不受此等 特定具體實施例限制。 實例1 使用由以重量計80%去鋁化之沸石Y ( 24.25埃之單位晶胞 尺寸及8 0之矽石/氧化鋁莫耳比）及以重量計20%之一種氧 化銘黏合劑组成之一種酸性載體。用一種過銖酸（HReO〇 水溶液浸潰此種載體之樣本以達到2 0重量％ Re02(對應於 17.1重量％iRe ;該重量百分比係以載體之重量爲基準）3 然後將部分地製備之催化劑於400°C乾燥及烺燒歷時2小 時，其後進行用H2PdCl4之一種水溶液浸漬以達到以重量計 5%之PdO含量（對應於以重量計4.3%之Pd)。最後，於350 eC於空氣中乾燥及烺燒已完成之催化劑歷時2小時，催化 劑係另外稱爲PdRe/Y。 -13- 本紙張尺度適用中國國家檁準（CNS ) Α4規格（210X297公釐） I--------赛------ΐτ------^ (請先聞讀背面之注意事項孑4寫本頁} d64687 A7 ----------B7 五、發明説明（11 ) 實例2_ 於一種反應器中安置由與80立方厘米之破化矽粒子 (SiC ’直徑0.21毫米）混合之2〇立方厘米之以上pdRe/Y组成 I 一種床。如此獲得之PdRe/Y床係根據於歐洲專利-A-〇, 181，254中揭示之方法預硫化。此種方法包括用於正庚烷 中稀釋之聚硫化二第三壬基浸潰、接著於l5(rC於氮之大氣 壓力下乾燥歷時2小時。其後催化劑係經由以於5〇〇標準升 (N1) /公斤之氣體速率之氫之協助而致使反應器達到巴 之總壓力而活化。於2小時之内提高溫度自周圍溫度至25〇 C ’接著引進進料及以1 0 °C /小時之速率自250T：提高溫度 至3 1 〇°C。維持310°C之溫度歷時1 〇〇小時。 於元成活化程序之後，將具有如於表I中表示之特性（Bp 係沸點’ IBP及FBP分別地意表初沸點及終沸點）之一種進 料通過PdRe/Y之床。進料係以重量計75%之一種直餾汽油 與以重量計25%之一種輕循環油之一種摻和物。方法條件包括 3 50°C之PdRe/Y床之重量平均床溫度（WABT)、50巴之總壓 力、500標準升/公斤之氣體速率及ί ο公斤/升小時之重量 每小時空間速度（WHSV)。 ----------^------1T------線 (請先聞讀背面之注意事項乒i.私本頁) 經濟部中央標準局負工消費合作社印製 表I 進料特.性 s (重量％) 1.37 沸點分布Ό N (重量ppm) 228 IBP 150 芳族烴(毫莫耳/100克） 10 229 單核 77.3 50 287 雙核 55.3 90 357 多核 20.4 FBP 424 "14- 本紙張尺度適用中國國家標牟（CNS ) A4規格（2I0X297公釐） 4 6 4b? 7 A7 ____ _B7 五、發明説明（12 ) 測定硫含量及氮含量（皆於重量ppm)、以具有比進料之初 沸點（即150°C )較低之沸點之生成物質之以重量計％表示之 裂解程度及單核、雙核及多核芳族烴之含量（以毫莫耳/100 克產物表示）。 結果係於表11中表示。 表II產物特性 產物 S (重量ppm) 519 N (重量ppm) 7.2 裂解(重量％150°C：) 2 芳族烴(毫莫耳/100克） 口 τί 1 « 早核 66.0 雙核 6.3 多核 3.0 經濟部中央標準局員工消費合作社印裝 自表II可看到，進料成分之裂解成爲低沸點物質係降低 至最低，而同時PdRe/Y催化劑之加氫脱硫活性及加氫脱氮 活性係優良的：硫含量及氮含量已係分別地以96.2%及 96.8%降低。 表Π亦顯示，芳族烴轉化作用係很良好的。關於此點， 應牢記多核（三及以上）芳族烴及雙核芳族烴之轉化作用最 初增加單核芳族烴含量。轉化率（以重量％表示）可係經由 假設芳族烴保由一種連續之反應通路氫化而計算，即假設 _____ -15- 本紙張尺度適财賴家縣（CNS )〜祕（2lQ>< 297公董） * /16 4 68 五 、發明説明（13 ) A7 B7 -—- 經濟部中央標準局員工消費合作社印製 =核芳族烴係轉化成爲雙核芳族烴、雙核芳族烴轉化成爲 單核芳族烴及單核芳族烴轉化成爲環烷族烴。由於已知當 於-種多核結構中之芳族環之數目降低時，於—種多核結 構中包含I一種芳族環之氫化作用通常變成動力學上較不 2的，因此此係一種正確之假[因此，於產物中發現之 單核芳族煙可來自三種來源：（i)來自於進料中存在之未轉 化之雙核芳族烴'(i i)來自原來已存在於進料中之經轉化 之雙核芳族烴及（iii)來自經轉化之雙核芳族烴，其，轉 而，來自於進料中存在之經轉化之多核芳族烴。基於連續 之通路機構學之基礎，發現多核芳族烴、雙核芳族烴及單 核芳族烴之轉化程度分別地係高至85.3%、91 3%及54 1%。 實例3 除了使用包含於由65重量％改質之滞石γ (24.32埃之單 位晶胞尺寸及9.2之矽石/氧化鋁莫耳比）與3 5重量％碎石组 成之一種酸性載體上之5重量％PdO(對應於4.3重量％I> d)及 5重量％ Re〇2(對應於4.3重量％ R e )之一種pdRe/Y催化劑以 外，重複實例2之程序。 進料係具有於下列之表ΠΙ中表示之性質、直餾汽油與輕 循環油之一種摻和物及除了於360°C之溫度以催化劑接觸進 料以外，使用之方法條件係與先前者完全相同。 ----------裝------.π------0 (請先閱讀背面之注意事項本頁} - 16- 6 4 經濟部中央標準局員工消費合作社印製 4 68 A7 B7 五、發明説明（14 ) 表III進料特性 S (重量ppm) 3900 沸點分布^： N (重量ppm) 320 IBP 196 芳族烴(毫莫耳/100克） 10 %wt 287 單核 54.4 50 %wt 358 雙核 24.8 90 %wt 403 三核 9.8 多核(三以上） 14.8 FBP 435 測定硫含量及氮含量（皆於重量p p m)、以具有低於15 (TC 之沸點之生成物質之以重量計％表示之裂解程度及單核' 雙核及三核芳族烴之百分比轉化率。 結果係於表IV中表示。 表IV產物特性 產物 S (重量ppm) 380 N (重量ppm) 39.0 裂解(重量％150°(：1 0.9 芳族烴轉化率(％) 單核 50.2 雙核 81.3 三核 73.1 ----------¾------.玎------.^ (請先閱讀背面.之注意事項寫本頁) . -17- 本紙張尺度適用中國國家標準（CNS ) A4规格（210X297公釐） 經濟部中央標準局貝工消費合作社印製* 1T Printed by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs 464687 A7 ________B7 V. Description of Invention (5) The carrier is known in this art. Therefore, for the purposes of the present invention, examples of suitable carriers include aluminosilicate or aluminosilicate beach stones, amorphous silica-alumina, alumina, fluorinated alumina, phyllosilicate Or an acidic carrier of a mixture of two or more of these substances. It will be noted that the type of acidic support used will depend primarily on the intended use of the catalyst. However, for most applications, it is preferred that the support comprises a zeolite. Examples of suitable zeolites are silicoaluminophosphates, such as SAPO-1, SAP0-31, and SAP0-41, and salt shoals such as forsterite, ZSM-5, ZSM-23, SSZ-32, Mordenite, beta-taolite, and octahedral shards such as octadecorite and synthetic spar. When the catalyst is used in a method for manufacturing a lubricating base oil, including a hydroconversion stage, for example, the use of silicoaluminophosphate can be considered. However, in general, the use of aluminosilicate zeolites is preferred. A particularly preferred aluminosilicate zeolite Y is usually used in a modified (ie de-named) form. In particular, when the catalyst according to the present invention is used as a hydrotreating catalyst for reducing the content of aromatic hydrocarbons and sulfur-containing and nitrogen-containing compounds, it is preferable to use an acidic support system containing a modified zeolite Y. . A particularly useful modified zeolite Y has a unit cell size of less than 24 6 0 Angstroms (preferably 24.20 to 24.45 Egypt, more preferably 24.20 to 24.35 Angstroms) and 5 or 10 to 50 (For example, from 5, 10 or 15 to or from 5, 10, 15 or 30 to 90) the Si02 / Al203 mole ratio in Fanyuan. Such carriers are known and examples in this art, for example, described in European Patent _A-0,247,678; European Patent-A-0,303,332; and European Patent-A-0,512,652. Can also be used appropriately to increase the content of rhenium metal (usually sodium) -8- This paper size applies Chinese National Standard (CNS) A4 grid (210X297 mm) '' 'f gutter {Please read the note on the back first Matters ri..w this page) Printed dG4687 A7 by the Consumer Cooperatives of the Central Bureau of Standards of the Ministry of Economic Affairs --------___ B7 V. Modification of the Invention Description (e) < Stones γ 'such as in European Patent _ 八 _〇 , 519,573. "In addition to any of the above-mentioned support materials, the support may also include a family of adhesive materials. The use of adhesives in catalyst supports is well known in the art and therefore, suitable adhesives include inorganic oxides such as silica. , Emulsified stone, crushed stone, alumina, boron oxide, zirconia, and titanium oxide, and clay. Among these, for the purpose of the present invention, the use of silica and / or alumina is preferred. Existing, based on the total weight of the carrier, the binder content of the carrier can vary from 5 to 95% by weight. In a preferred embodiment, the carrier contains 10 to 60% by weight of the adhesive It has been found that a binder content of 10 to 40% by weight is particularly advantageous. The catalyst according to the invention can be used in various hydroconversion processes where a hydrocarbon feed containing aromatic compounds is at a high level. Contact with the catalyst in the presence of temperature and pressure hydrogen. Specific examples of these methods are hydrocoating, lubricating oil manufacturing (argon cracking / hydroisomerization), and hydrotreating. The present invention is also about On one side For the use of the catalyst mentioned above, a hydrocarbon feed containing aromatic compounds in the method is in contact with the catalyst under the presence of high temperature and pressure in the presence of hydrogen. Since the catalyst is not only used in hydrotreating aromatic compounds, Furthermore, it is political in the purification of pure nitrogen and / or nitrogen compounds. Therefore, hydrocarbon feed systems containing sparse and / or nitrogen-containing compounds in addition to aromatic compounds are particularly suitable due to the excellent properties of the catalysts according to the present invention. Hydrotreating performance, so the catalyst according to the present invention is particularly useful as a first stage catalyst in a two-stage hydrocracking process. Then, the second stage catalyst is a dedicated hydrocracking catalyst. _____- 9- This The paper size is applicable to China National Private Standard (CNS) A4 specification (21〇297297); ---------- Dream ------ 1Γ ------ Φ (谙 Read the back first .Notes on this page) (llsr page) 464687 A7 B7 Production and cooperation of employees of the Central Bureau of Standards of the Ministry of Economic Affairs Du printed 5. Description of the invention (7) In the manufacturing method of the lubricating base oil, 'may include at least one hydroconversion stage' Remove sulfur and / Or nitrogen contamination, and / or hydrogenated aromatics, and / or hydroisomerized linear and slightly branched hydrocarbons to further branched hydrocarbons, and / or hydrocracking waxy molecules (usually long chains) Stone soil molecules or molecules containing tails of this type) become smaller molecules. For use in these lubricating base oil manufacturing methods, the catalysts according to the invention will preferably contain a carrier 'which contains amorphous silicon Stone—alumina, oxidized oxide of Xianghua or a zeolite with "Xishi Stone and / or Oxide Ming as a binder. If the hydrotreating reaction is mainly planned, the use of a carrier containing modified zeolite γ is more If the cracking and / or hydroisomerization of the waxy molecule is the main purpose, then the preferred carrier comprises fluorinated alumina, amorphous silica-alumina or pyroclastic, such as magnesite sludge, ZSM_5, 2SM-23, SSZ-32 and SAPO-Π. A hydroconversion stage in a method for manufacturing a lubricating base oil typically involves contacting a suitable catalyst in the presence of hydrogen at a temperature between 200 and 450 ° C and a pressure of up to 200 bar—a lubricant is fed material. Examples of a method for producing a lubricating base oil in which the catalyst according to the present invention can be used are disclosed in British Patent _Α_1ι546 > 504 and European Patent -A-0,178,710. It has been found that the catalyst system according to the invention is particularly suitable for use in a hydrotreating process. Suitable hydroprocessing operating conditions are a temperature in the range of 20 to 450 ° C (preferably 210 to 350 or 400 ° C), and a range of 10 to 200 bar (preferably 25 to 100 bar). Total pressure within. Examples of suitable argon treatment methods are described in European Patent Application Publication Nos. 0,553,920 and 0,611,816. Suitable for this kind of hydroprocessing method-10- ---------- ^ ------ ΪΤ ------ ^ (Please read the precautions on the back first to write this page )-This paper size applies to China National Standards (CNS > A4 size (210X297mm) A7 B7 V. Description of invention (8) The printed materials produced by the Consumer Cooperatives of the Central Standards and Quarantine Bureau of the Ministry of Economic Affairs are produced by catalytically cracked gasoline and gasoline. Gas oil, light gas oil, thermal and / or catalytic cracking distillation oil (such as light cycle oil and cracking cycle oil) and a mixture of two or more of these oils. Many of these feeds usually include At least 70% of hydrocarbons boiling between 150 and 450 ° C. When used in this type of hydrogenation catalyst, it is preferred that the carrier contain a binder in the amount indicated above in the case of hydrotreating The preferred acidic material in the carrier is a zeolite γ that is the best modified salt zeolite. It has been found that the catalyst still shows excellent performance even in the presence of substantial amounts of sulfur and nitrogen-containing compounds. Its hydrotreating activity is particularly effective for hydrotreating mononuclear aromatic hydrocarbons. In addition, The catalyst is also very effective for the hydrogenation of dinuclear aromatic hydrocarbons and higher aromatic hydrocarbons (two or more polynuclear aromatic hydrocarbons). The present invention also relates to a method for preparing the above-mentioned catalyst, the method comprising Catalysis or ion exchange technology, followed by drying and scorching, and pre-sulfiding if necessary, combine the catalytically active metals into the refractory oxide support. In order to obtain a catalyst with particularly good catalytic activity, the method can be carried out through the following stages: (a) impregnating the carrier with one or more solutions containing a noble gold compound selected from the group consisting of platinum, palladium and iridium, and one or more solutions containing a tritium compound, if necessary, having Intermediate drying and / or smoldering; and (b) drying and simmering the impregnated carrier at a temperature within the range of 2 to 6 thieves. A preferred method of impregnating the carrier is a so-called pore volume method It includes treating a carrier with an impregnating solution in the volume of the seed type, wherein the size of the impregnating solution is -11. The paper scale is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm (please first Read the notes on the back- ,. I, ΦΓ This page j -------- line --- I --- 4 S 4 6 8 Printed by Employee Consumer Cooperative of Central Bureau of Standards, Ministry of Economic Affairs Α7 Β7 5 Explanation of the invention (9) The volume is substantially equal to the pore volume of the carrier. In this way, the complete use of the impregnation solution is achieved. It has been found that this impregnation method is particularly suitable because the resulting catalyst exhibits particularly good performance. For the purposes of the present invention, the impregnation stage (a) may be performed using one impregnation solution containing all metal components or may be performed in two separate impregnation stages for use with platinum and / or palladium and / or grades One stage of impregnation and one stage for impregnation with manganese and / or rhenium may have an intermediate drying and / or scorch stage. The metal compounds which can be used in the impregnating solution for preparing the catalyst according to the invention are known in the art. Typical manganese compounds are salts such as manganese sulfate, manganese nitrate, and manganese acetate that are soluble in water. Typical baht compounds are pergallic acid, ammonium perchain, and potassium perbaate. Typical palladium compounds used in impregnation solutions are tetragas palladium acid (H2PdCl4), palladium nitrate, vaporized palladium (II) and amine complexes thereof. H2PdCl4t is preferred. Typical platinum compounds used in an impregnating solution are hexamethylene acid (H2PtCl6), transammonium hydroxide, and suitable amine amine complexes in the presence of hydrogen acid as needed. In the catalyst preparation, the catalyst is burned in the air in the final stage, so that the metal becomes the form of their oxides, which is a common example. In order to at least partially convert the metals into their sulfides, the catalyst may be presulfided after the final calcination stage and before contact with the feed. Suitable presulfidation methods are known in the art, such as, for example, from European Patent Application Announcement No. 0,181,254; 〇, 329,499; 〇, 448,435 and 〇, 564,317 and International Patent Application Announcement World Intellectual Property Organization Patent No. 93/02793 and World Intellectual Property Organization Patent No. 94/25157. -12- The size of this paper is applicable to the Chinese National Standard (CNS) A4 (2 丨 〇χ297) ¾1T ------. ^ (Please read the precautions on the back first, then this tile) Central Bureau of Standards, Ministry of Economic Affairs Printed by employees' consumer cooperatives A7 B7 V. Description of invention (ίο) Therefore, in another embodiment of the present invention, the method for preparing a catalyst includes the following additional stages: (c) The dried and calcined catalyst is subjected to A pre-curing treatment. In addition to the pre-vulcanization methods described above, pre-vulcanization can also occur through on-site pre-vulcanization. This includes contacting a calcined catalyst with a sulfur-containing hydrocarbon feed under suitable conditions, generally under conditions that are less severe than those applied during the intended operation. The catalyst according to the invention can be regenerated via methods known in the art. A typical method for recovering catalytically active metals from a spent catalyst involves removing the activated catalyst from the reactor, washing the catalyst to remove hydrocarbons', burning off coke and subsequently recovering precious metals and manganese and / or plutonium. The invention is illustrated by the following examples, but the invention is not limited by these specific embodiments. Example 1 A composition consisting of 80% by weight of aluminized zeolite Y (unit cell size of 24.25 Angstroms and silica / alumina mole ratio of 80) and 20% by weight of an oxide binder An acidic carrier. A sample of this carrier is impregnated with a perbasic acid (HReO 0 aqueous solution to reach 20% by weight Re02 (corresponding to 17.1% by weight iRe; the weight percentage is based on the weight of the support) 3 and then a partially prepared catalyst Drying and simmering at 400 ° C for 2 hours, followed by impregnation with an aqueous solution of H2PdCl4 to reach a PdO content of 5% by weight (corresponding to 4.3% by weight of Pd). Finally, air was used at 350 eC. The finished catalyst for intermediate drying and sintering took 2 hours, and the catalyst is also called PdRe / Y. -13- This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) I ------ -赛 ------ ΐτ ------ ^ (Please read and read the notes on the back 孑 4 write this page} d64687 A7 ---------- B7 V. Description of the invention ( 11) Example 2_ A bed consisting of pdRe / Y of more than 20 cm3 mixed with 80 cm3 of cracked silicon particles (SiC 'diameter 0.21 mm) was placed in a reactor. I obtained a PdRe / Y bed It is prevulcanized according to the method disclosed in European Patent-A-〇, 181,254. This method includes a method for diluting n-heptane. The polysulfide was immersed in the second and third nonyl groups, and then dried at 15 (rC under atmospheric pressure of nitrogen for 2 hours. The catalyst was then assisted by hydrogen at a gas rate of 500 N (N1) / kg. The reactor was activated by reaching a total pressure of bar. Within 2 hours, the temperature was increased from the ambient temperature to 25 ° C. Then the feed was introduced and the temperature was increased from 10 ° C / hour to 250T: the temperature was increased to 3 1 °. ° C. Maintained a temperature of 310 ° C for 100 hours. After the Yuancheng activation procedure, it will have the characteristics as shown in Table I (Bp is the boiling point 'IBP and FBP mean the initial and final boiling points respectively). A feed is passed through a bed of PdRe / Y. The feed is a blend of 75% by weight of a straight run gasoline and 25% by weight of a light cycle oil. Process conditions include 3 50 ° C PdRe / Y bed weight average bed temperature (WABT), total pressure of 50 bar, gas rate of 500 standard liters / kg and weight hourly space velocity (WHSV) of ο kg / liter hour. -------- -^ ------ 1T ------ line (please read the notes on the back first i. Private page) Central Bureau of Standards, Ministry of Economic Affairs Printed by Industrial and Commercial Cooperatives I Feed characteristics. Weight (% by weight) 1.37 Boiling point distribution Ό N (ppm by weight) 228 IBP 150 Aromatic hydrocarbon (mmol / 100g) 10 229 Single core 77.3 50 287 Dual core 55.3 90 357 Multi-core 20.4 FBP 424 " 14- This paper size applies to China National Standards (CNS) A4 specifications (2I0X297 mm) 4 6 4b? 7 A7 ____ _B7 V. Description of the invention (12) Determination of sulfur content and nitrogen content (both (Ppm by weight), the degree of cracking expressed by weight% and the content of mononuclear, binuclear, and polynuclear aromatic hydrocarbons (in milliseconds) expressed as% by weight of the produced substance having a lower boiling point than the initial boiling point of the feed (ie 150 ° C) Moore / 100 g product). The results are shown in Table 11. Table II Product characteristics Product S (ppm by weight) 519 N (ppm by weight) 7.2 Pyrolysis (150% by weight: 150 ° C :) 2 Aromatic hydrocarbons (millimol / 100 g) τί 1 «Early core 66.0 dual core 6.3 multi core 3.0 economic Printed by the Consumer Cooperative of the Ministry of Standards of the People's Republic of China. It can be seen from Table II that the cracking of the feed ingredients to a low boiling point system is minimized, and at the same time the PdRe / Y catalyst has excellent hydrodesulfurization and hydrodenitrogenation activity : Sulfur content and nitrogen content have been reduced by 96.2% and 96.8%, respectively. Table II also shows that the aromatic hydrocarbon conversion system is very good. In this regard, it should be kept in mind that the conversion of polynuclear (three and above) aromatic hydrocarbons and dinuclear aromatic hydrocarbons initially increases the content of mononuclear aromatic hydrocarbons. Conversion rate (expressed by weight%) can be calculated by assuming that aromatic hydrocarbons are hydrogenated by a continuous reaction pathway, that is, assuming _____ -15- This paper is suitable for Laijia County (CNS) ~ Secret (2lQ > < 297 public directors) * / 16 4 68 V. Description of the invention (13) A7 B7 ------ Printed by the Consumer Cooperatives of the Central Standards Bureau of the Ministry of Economic Affairs = Conversion of nuclear aromatic hydrocarbons to dinuclear aromatic hydrocarbons, conversion of dinuclear aromatic hydrocarbons It becomes a mononuclear aromatic hydrocarbon and a mononuclear aromatic hydrocarbon is converted into a naphthenic hydrocarbon. Since it is known that when the number of aromatic rings in a multi-core structure decreases, the hydrogenation of an aromatic ring containing I in a multi-core structure usually becomes less kinetically, so this is a correct False [Therefore, the mononuclear aromatic smoke found in the product can come from three sources: (i) from unconverted dinuclear aromatic hydrocarbons present in the feed '(ii) from the raw materials already present in the feed The converted dinuclear aromatic hydrocarbons and (iii) are from the converted dinuclear aromatic hydrocarbons, which, in turn, are from the converted polynuclear aromatic hydrocarbons present in the feed. Based on the continuous pathway mechanism, it was found that the conversion degrees of polynuclear aromatic hydrocarbons, dinuclear aromatic hydrocarbons, and mononuclear aromatic hydrocarbons were as high as 85.3%, 91 3%, and 54 1%, respectively. Example 3 In addition to using an acidic carrier consisting of 65% by weight of modified stamenite γ (unit cell size of 24.32 Angstroms and silica / alumina mole ratio of 9.2) and 35% by weight crushed stone The procedure of Example 2 was repeated except for a pdRe / Y catalyst of 5% by weight PdO (corresponding to 4.3% by weight I > d) and 5% by weight ReO2 (corresponding to 4.3% by weight Re). The feed has the properties shown in Table III below, a blend of straight run gasoline and light cycle oil, and the conditions of the method used are completely the same as those of the former except that the catalyst is contacted with the feed at a temperature of 360 ° C. the same. ---------- Installation ------. Π ------ 0 (Please read the note on the back page first)-16- 6 4 Staff Consumer Cooperatives, Central Bureau of Standards, Ministry of Economic Affairs Printed 4 68 A7 B7 V. Description of the invention (14) Table III Feed characteristics S (ppm by weight) 3900 Boiling point distribution ^: N (ppm by weight) 320 IBP 196 Aromatic hydrocarbon (millimoles / 100 g) 10% wt 287 Single-core 54.4 50% wt 358 Dual-core 24.8 90% wt 403 Tri-core 9.8 Multi-core (three or more) 14.8 FBP 435 Determination of sulfur content and nitrogen content (both by weight ppm), with a substance having a boiling point below 15 (TC) The degree of cracking expressed in% by weight and the percentage conversion of single-core 'binuclear and trinuclear aromatic hydrocarbons. The results are shown in Table IV. Table IV Product Characteristic Product S (ppm by weight) 380 N (ppm by weight) 39.0 Cracking (wt% 150 ° (: 1 0.9 aromatic conversion) (%) single core 50.2 dual core 81.3 triple core 73.1 ---------- ¾ ------. 玎 ----- -. ^ (Please read the note on the back. Write this page first). -17- This paper size is applicable to China National Standard (CNS) A4 (210X297 mm) Printed by the Bayer Consumer Cooperative of the Central Standards Bureau of the Ministry of Economic Affairs
4 C B A7 B7 五、發明説明（15 ) 實例4 除了方法係以經由提高方法溫度至380°C之溫和之加氫裂 解方式（對照實例3之加氫處理方式）進行以外，重複實例3 之程序。所有之其他方法條件維持相同。 測定硫含量及氮含量（皆於重量p p m )、以具有低於150°C 之沸點之生成物質之以重量計％表示之裂解程度、單核、 雙核及三核芳族烴之百分比轉化率及傾注點。 結困係於表V中表示。 I---------參------.π!-----^ (請先閲讀背面之注意事項-fi,寫本頁) - - -18- 表V 產物特性 產物 S (重量ppm) 24 N (重量ppm) <1 裂解(重量％150°(：_) 18.9 芳族烴轉化率。/〇 單核 44.0 雙核 85.1 三核 85.1 *傾注點(°C ) 3 *進料之傾注點係1 5 °C。 本紙張尺度適用中圉國家標準（CNS ) A4規格（2IOX297公釐）4 CB A7 B7 V. Description of the Invention (15) Example 4 The procedure of Example 3 was repeated except that the method was performed by a mild hydrocracking method (comparing to the hydrotreating method of Example 3) by increasing the method temperature to 380 ° C. . All other method conditions remain the same. Determination of sulfur content and nitrogen content (both in ppm by weight), degree of cracking expressed in% by weight of produced substances having boiling points below 150 ° C, percentage conversion rates of mono-, di- and tri-nuclear aromatic hydrocarbons, and Pour points. The results are shown in Table V. I --------- see ------. Π! ----- ^ (Please read the note on the back-fi first, write this page)---18- Table V Product Characteristics Product S (ppm by weight) 24 N (ppm by weight) < 1 Pyrolysis (150% by weight 150 ° (: _) 18.9 Aromatic conversion. / 0 single core 44.0 dual core 85.1 triple core 85.1 * pour point (° C) 3 * The pour point of the feed is 15 ° C. The paper size is applicable to the China National Standard (CNS) A4 specification (2IOX297 mm)